Boron was incorporated into GaN in order to determine its limits of solubility, its ability of reducing the lattice constant mismatch with 6H-SiC, as well as its effects on the structural and optical properties of GaN epilayers. BxGa1−xN films were deposited on 6H-SiC (0001) substrates at 950 °C by low pressure MOVPE using diborane, trimethylgallium, and ammonia as precursors. A single phase alloy with x=0.015 was successfully produced at a gas reactant B/Ga ratio of 0.005. Phase separation into pure GaN and BxGa1−xN alloy with x=0.30 was deposited for a B/Ga reactant ratio of 0.01. This is the highest B fraction of the wurtzite structure alloy ever reported. For B/Ga ratio ≥ 0.02, no BxGa1−xN was formed, and the solid solution contained two phases: wurtzite GaN and BN based on the results of Auger and x-ray diffraction. The band edge emission of BxGa1−xN varied from 3.451 eV for x=0 with FWHM of 39.2 meV to 3.465 eV for x=0.015 with FWHM of 35.1 meV. The narrower FWHM indicated that the quality of GaN epilayer was improved with small amount of boron incorporation.